WO2004056914A1 - Matiere polyester a mouler electriquement isolante et thermoconductrice - Google Patents

Matiere polyester a mouler electriquement isolante et thermoconductrice Download PDF

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Publication number
WO2004056914A1
WO2004056914A1 PCT/EP2003/014281 EP0314281W WO2004056914A1 WO 2004056914 A1 WO2004056914 A1 WO 2004056914A1 EP 0314281 W EP0314281 W EP 0314281W WO 2004056914 A1 WO2004056914 A1 WO 2004056914A1
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weight
molding compositions
thermoplastic molding
component
compositions according
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PCT/EP2003/014281
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German (de)
English (en)
Inventor
Michael GEPRÄGS
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Basf Aktiengesellschaft
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Priority to AU2003293893A priority Critical patent/AU2003293893A1/en
Publication of WO2004056914A1 publication Critical patent/WO2004056914A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3737—Organic materials with or without a thermoconductive filler
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the invention relates to thermoplastic molding compositions containing
  • thermoplastic polyester A) 10 to 70 wt .-% of a thermoplastic polyester
  • the invention relates to the use of the molding compositions according to the invention for the production of fibers, films and moldings of any kind, and to the moldings obtainable here.
  • connection units generally consist of heat-conducting pastes and an electrical insulator (mica flakes or aluminum oxide flakes).
  • Heating elements have a similar structure.
  • a design consists of an electrical heating element and a heat-conducting substrate.
  • the heating element is a metallic resistance wire that has to be introduced into the heat-conducting substrate.
  • connection units and chips have different expansion coefficients.
  • the production of such an element is correspondingly complex.
  • Replacing the connection units and also the metal parts in these elements with plastics is problematic since, in addition to a high thermal conductivity, an electrically insulating property of the thermoplastic composition is also imperative.
  • the surface should above all be smooth, printable, markable and have sufficient hardness and surface roughness, which can usually only be achieved on a limited scale with high filler contents (due to sufficient conductivity).
  • the present invention was therefore based on the object of providing thermoplastic polyester molding compositions which have good flowability / thermal conductivity and at the same time have an electrically insulating property.
  • the surface of the molded parts should be smooth and versatile. Accordingly, the molding compositions defined at the outset were found. Preferred embodiments can be found in the subclaims.
  • the molding compositions according to the invention contain 10 to 70, preferably 15 to 95 and in particular 20 to 44.9% by weight of a thermoplastic polyester as component (A).
  • Polyesters A) based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound are generally used.
  • a first group of preferred polyesters are polyalkylene terephthalates, in particular with 2 to 10 carbon atoms in the alcohol part.
  • Such polyalkylene terephthalates are known per se and are described in the literature. They contain an aromatic ring in the main chain, which comes from the aromatic dicarboxylic acid.
  • the aromatic ring can also be substituted, for example by halogen such as chlorine and bromine or by C 1 -C 4 alkyl groups such as methyl, ethyl, i- or n-propyl and n-, i- or t-butyl groups.
  • polyalkylene terephthalates can be prepared in a manner known per se by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxy compounds.
  • Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof.
  • Up to 30 mol%, preferably not more than 10 mol%, of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids.
  • diols having 2 to 6 carbon atoms in particular 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclohexanediol, 1 , 4-Cyclohexanedimethanol and neopentyl glycol or mixtures thereof are preferred.
  • polyesters (A) are polyalkylene terephthalates which are derived from alkanediols having 2 to 6 carbon atoms. Of these, particularly preferred are polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof. Also preferred are PET and / or PBT, which contain up to 1% by weight, preferably up to 0.75% by weight, of 1,6-hexanediol and / or 2-methyl-1,5-pentanediol as further monomer units.
  • the viscosity number of the polyesters (A) is generally in the range from 50 to 220, preferably from 80 to 160 (measured in a 0.5% strength by weight solution in a phenol / o-dichlorobenzene mixture (weight ratio 1: 1 at 25 ° C) according to ISO 1628.
  • Particularly preferred are polyesters whose carboxyl end group content is up to 100 meq / kg, preferably up to 50 meq / kg and in particular up to 40 meq / kg polyester.
  • Such polyesters can be produced, for example, by the process of DE-A 4401 055.
  • the carboxyl end group content is usually determined by titration methods (eg potentiometry).
  • Particularly preferred molding compositions contain, as component A), a mixture of polyesters other than PBT, such as, for example, polyethylene terephthalate (PET).
  • PBT polyethylene terephthalate
  • the proportion e.g. The polyethylene terephthalate in the mixture is preferably up to 50, in particular 10 to 35,% by weight, based on 100% by weight of A).
  • PET recyclates also called scrap PET
  • PBT polyalkylene terephthalates
  • So-called post industrial recyclate this is production waste from polycondensation or processing e.g. Sprues in injection molding processing, approach goods in injection molding processing or extrusion or edge sections of extruded sheets or foils.
  • Post consumer recyclate these are plastic items that are collected and processed by the end consumer after use.
  • the most dominant item in terms of quantity are blow-molded PET bottles for mineral water, soft drinks and juices.
  • Both types of recyclate can either be in the form of regrind or in the form of granules. In the latter case, the pipe cyclates are melted and granulated in an extruder after separation and cleaning. This usually facilitates handling, flowability and meterability for further processing steps.
  • Recyclates both granulated and in the form of regrind, can be used, the maximum edge length being 10 mm, preferably less than 8 mm.
  • the residual moisture content after drying is preferably ⁇ 0.2%, in particular ⁇ 0.05%.
  • Aromatic dicarboxylic acids are the compounds already described for the polyalkylene terephthalates. Mixtures of 5 to 100 mol% isophthalic acid and 0 to 95 mol% terephthalic acid are preferred, in particular mixtures of about 80% terephthalic acid. acid with 20% isophthalic acid to about equivalent mixtures of these two acids used.
  • the aromatic dihydroxy compounds preferably have the general formula
  • Z represents an alkylene or cycloalkylene group with up to 8 C atoms, an arylene group with up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in which m is from 0 to 2 has.
  • the compounds can also carry C 1 -C 6 -alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents on the phenylene groups.
  • Polyalkylene terephthalates and fully aromatic polyesters can of course also be used. These generally contain 20 to 98% by weight of the polyalkylene terephthalate and 2 to 80% by weight of the fully aromatic polyester.
  • polyester block copolymers such as copolyether esters can also be used.
  • Such products are known per se and are known in the literature, e.g. in US-A 3,651,014.
  • Corresponding products are also available commercially, e.g. Hytrel® (DuPont).
  • polyester should also be understood to mean halogen-free polycarbonates.
  • Suitable halogen-free polycarbonates are, for example, those based on diphenols of the general formula
  • Q is a single bond, a C, - to C 8 -alkylene, a C 2 - to C 3 -alkylidene, a Gabis C 6 -cycloalkylidene group, a C 6 - to C 12 -arylene group and -O-, -S - or -SO 2 - and m is an integer from 0 to 2.
  • the diphenols can also have substituents on the phenylene radicals, such as C 1 -C 6 -alkyl or C 1 -C 6 -alkoxy.
  • Preferred diphenols of the formula are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1, 1 bis (4-hydroxyphenyl) -cyclohexane.
  • 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) -3,3,5- are particularly preferred. trimethylcyclohexane.
  • both homopolycarbonates and copolycarbonates are suitable as component A; in addition to the bisphenol A homopolymer, the copolycarbonates of bisphenol A are preferred.
  • the suitable polycarbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of at least trifunctional compounds, for example those having three or more than three phenolic compounds OH groups.
  • Polycarbonates which have relative viscosities ⁇ rei of 1.10 to 1.50, in particular of 1.25 to 1.40, have proven to be particularly suitable. This corresponds to average molecular weights M w (weight average) of 10,000 to 200,000, preferably from 20,000 to 80,000 g / mol.
  • M w weight average
  • the diphenols of the general formula are known per se or can be prepared by known processes.
  • the polycarbonates can be prepared, for example, by reacting the diphenols with phosgene by the interfacial process or with phosgene by the process in a homogeneous phase (the so-called pyridine process), the molecular weight to be set in each case being achieved in a known manner by a corresponding amount of known chain terminators. (Regarding polydiorganosiloxane-containing polycarbonates, see for example DE-OS 33 34 782).
  • Suitable chain terminators are, for example, phenol, pt-butylphenol but also long-chain alkylphenols such as 4- (1,3-tetramethylbutyl) phenol, according to DE-OS 2842 005 or monoalkylphenols or dialkylphenols with a total of 8 to 20 carbon atoms in the Alkyl substituents according to DE-A 35 06472, such as p-nonylphenyl, 3,5-di-t-butylphenol, pt-octylphenol, p-dodecylphenol, 2- (3,5-dimethy! -Heptyl) -phenol and 4- (3rd , 5-dimethylheptyl) -phenol.
  • alkylphenols such as 4- (1,3-tetramethylbutyl) phenol, according to DE-OS 2842 005 or monoalkylphenols or dialkylphenols with a total of 8 to 20 carbon atoms in the Alkyl substitu
  • Halogen-free polycarbonates in the sense of the present invention means that the polycarbonates are composed of halogen-free diphenols, halogen-free chain terminators and optionally halogen-free branching agents, the content of minor ppm amounts of saponifiable chlorine resulting, for example, from the production of the polycarbonates with phosgene by the phase interface process. is not to be regarded as containing halogen in the sense of the invention.
  • Such polycarbonates with ppm contents of saponifiable chlorine are halogen-free polycarbonates in the sense of the present invention.
  • Amorphous polyester carbonates may be mentioned as further suitable components A), phosgene being replaced by aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units during production.
  • aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units during production.
  • Bisphenol A can also be replaced by Bisphenol TMC.
  • Such polycarbonates are available under the trademark APEC HT® from Bayer.
  • the molding compositions according to the invention contain 30 to 85, preferably 40 to 85 and in particular 55 to 80% by weight of an aluminum oxide.
  • the component B) preferably has an average particle size (d 5 o value) of less than 20 microns, preferably less than 10 microns.
  • a d 50 value is generally understood by the person skilled in the art to mean the particle size value, in which 50% of the particles have a smaller particle size and 50% have a larger particle size.
  • the d 10 value is preferably less than 10 ⁇ m, in particular less than 5 ⁇ m and very particularly preferably less than 2.2 ⁇ m.
  • Preferred d go values are less than 50 ⁇ m and in particular less than 30 ⁇ m and very particularly preferably less than 30 ⁇ m.
  • the oxides occur in various modifications, of which the hexagonal ⁇ -oxide is the only thermodynamically stable modification.
  • the face-centered cubic -AI 2 0 3 is also well characterized. It arises from the aluminum hydroxides by heating to 400-800 ° C and, like the other modifications, can be converted to -.- Al 2 0 3 by annealing to over 1100 °.
  • Jff-AI 2 0 3 is a group of oxides that contain small amounts of foreign ions in the crystal lattice.
  • Other modifications like the numerous transitional forms between the aluminum hydroxides and the two, are of lesser importance.
  • ⁇ -Al 2 0 3 density 3.98, hardness 9, mp. 2053 °, which is insoluble in water, acids and. Bases is.
  • the ⁇ -AI 2 0 3 is obtained from bauxite using the Bayer process.
  • the main amount is used for the electrolytic production of aluminum.
  • the oxides are a thin protective layer on aluminum; this oxide layer can be reinforced by chemical or anodic oxidation.
  • ⁇ -AI 2 0 3 occurs as corundum, mp 2050 °. Corundum is mostly clouded by impurities and often also colored. Today, corundum is technically extracted as electrical corundum; this melts Al 2 0 3 obtained from bauxite. in the electric arc furnace over 2000 °. This gives a very hard product with about 99% ⁇ -AI 0 3 .
  • active oxides are obtained by precipitation processes from aluminum salt solution - e.g. B. over thermally post-treated aluminum hydroxide gels - or by calcination from a-aluminum hydroxide at low temperatures or by shock heating.
  • Component B) preferably has a specific surface area according to BET (according to DIN 60 132 or ASTM D 3037) of at least 0.1, preferably 0.3 m 2 / g.
  • the preferred density is 2.5 to 4.5, in particular 3.9 to 4.0 g / an 3 .
  • the sodium oxide content is preferably less than 0.4, in particular from 0.10 to 0.35% by weight, based on 100% by weight of B).
  • the thermal conductivity according to DIN 52612 is preferably at least 20 W / mK and in particular at least 25 W / mK.
  • the molding compositions according to the invention can contain 0 to 5, preferably 0.05 to 3 and in particular 0.1 to 2% by weight of at least one ester or amide of saturated or unsaturated aliphatic carboxylic acids with 10 to 40, preferably 16 to 22, Contain atoms with aliphatic saturated alcohols or amines with 2 to 40, preferably 2 to 6, carbon atoms.
  • the carboxylic acids can be 1- or 2-valent. Examples include pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and particularly preferably stearic acid, capric acid and montanic acid (mixture of fatty acids with 30 to 40 carbon atoms).
  • the aliphatic alcohols can be 1- to 4-valent.
  • examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, with glycerol and pentaerythritol being preferred.
  • the aliphatic amines can be 1- to 3-valent. Examples include stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, ethylenediamine and hexamethylenediamine being particularly preferred.
  • Preferred esters or amides are correspondingly glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate.
  • Mixtures of different esters or amides or esters with amides can also be used in combination, the mixing ratio being arbitrary.
  • the molding compositions according to the invention can contain 0 to 60, in particular up to 50% by weight of further additives and processing aids which are different from B) and / or C).
  • Customary additives D are, for example, in amounts of up to 40, preferably up to 30% by weight of rubber-elastic polymers (often also referred to as impact modifiers, elastomers or rubbers).
  • these are copolymers which are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or methacrylic acid esters with 1 to 18 carbon atoms in the alcohol component.
  • EPM ethylene-propylene
  • EPDM ethylene-propylene-diene
  • EPM rubbers generally have practically no more double bonds, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.
  • diene monomers for EPDM rubbers are conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-1,4-diene, hexa-1,4-diene, hexa-1,5 -diene, 2,5-dimethylhexa-1,5-diene and octa-1, 4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene, and alkenylnorbomenes such as 5-ethylidene-2-norbornene, 5-butylidene- 2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclo
  • the diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8,% by weight, based on the total weight of the rubber.
  • EPM or EPDM rubbers can preferably also be grafted with reactive carboxylic acids or their derivatives.
  • reactive carboxylic acids or their derivatives e.g. Acrylic acid, methacrylic acid and their derivatives, e.g. Glycidyl (meth) acrylate, as well as maleic anhydride.
  • Another group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or the esters of these acids.
  • the rubbers can also contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, e.g. Contain esters and anhydrides, and / or monomers containing epoxy groups.
  • dicarboxylic acid derivatives or monomers containing epoxy groups are preferably incorporated into the rubber by adding monomers of the general formulas I or II or III or IV containing dicarboxylic acid or epoxy groups to the monomer mixture
  • R 1 to R 9 represent hydrogen or alkyl groups having 1 to 6 carbon atoms and m is an integer from 0 to 20, g is an integer from 0 to 10 and p is an integer from 0 to 5
  • the radicals R 1 to R 9 are preferably hydrogen, where m is 0 or 1 and g is 1.
  • the corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.
  • Preferred compounds of the formulas I, II and IV are maleic acid, maleic anhydride and epoxy group-containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate, glycidyl methacrylate and the esters with tertiary alcohols, such as t-butyl acrylate. Although the latter have no free carboxyl groups, their behavior comes close to that of the free acids and is therefore referred to as monomers with latent carboxyl groups.
  • the copolymers advantageously consist of 50 to 98% by weight of ethylene, 0.1 to 20% by weight of monomers containing epoxy groups and / or monomers containing methacrylic acid and / or monomers containing acid anhydride groups and the remaining amount of (meth) acrylic acid esters.
  • Copolymers of are particularly preferred
  • n-butyl acrylate 1 to 45, in particular 10 to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate.
  • esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters.
  • vinyl esters and vinyl ethers can also be used as comonomers.
  • the ethylene copolymers described above can be prepared by processes known per se, preferably by random copolymerization under high pressure and elevated temperature. Appropriate methods are generally known.
  • Preferred elastomers are also emulsion polymers, the production of which e.g. is described in Blackley in the monograph "Emulsion Polymerization".
  • the emulsifiers and catalysts that can be used are known per se.
  • homogeneous elastomers or those with a shell structure can be used.
  • the shell-like structure is determined by the order of addition of the individual monomers;
  • the morphology of the polymers is also influenced by this order of addition.
  • the monomers for the production of the rubber part of the elastomers are only representative of acrylates such as n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof. These monomers can be combined with other monomers such as styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylic acid. ten such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate are copolymerized.
  • the soft or rubber phase (with a glass transition temperature of below 0 ° C) of the elastomers can represent the core, the outer shell or a middle shell (in the case of elastomers with more than two shells); in the case of multi-layer elastomers, several shells can also consist of a rubber phase.
  • one or more hard components are involved in the construction of the elastomer, these are generally obtained by polymerizing styrene, acrylonitrile, methacrylonitrile, methyl methyl styrene, methyl styrene, Acrylic acid esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate are produced as main monomers. In addition, smaller proportions of further comonomers can also be used here.
  • emulsion polymers which have reactive groups on the surface.
  • groups are e.g. Epoxy, carboxyl, latent carboxyl, amino or amide groups as well as functional groups by the use of monomers of the general formula
  • R 10 is hydrogen or a C r to C 4 alkyl group
  • R 11 is hydrogen, a C to C 8 alkyl group or an aryl group, in particular phenyl,
  • R 12 is hydrogen, ad to C 10 alkyl, a C 6 to C 2 aryl group or -OR 13
  • R is a C to C 8 alkyl or C 6 to C 12 aryl group, which can optionally be substituted by O- or N-containing groups,
  • X is a chemical bond, a C r to C 10 alkylene or C 6 -C 12 arylene group or O
  • Z is a C 1 to C 10 alkylene or C 6 to C 2 arylene group.
  • the graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups on the surface.
  • acrylamide, methacrylamide and substituted esters of acrylic acid or methacrylic acid such as (Nt-butylamino) ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) methyl acrylate and (N, N- Diethylamino) called ethyl acrylate.
  • the particles of the rubber phase can also be crosslinked.
  • Monomers acting as crosslinking agents are, for example, buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and the compounds described in EP-A 50 265.
  • So-called graft-linking monomers can also be used, i.e. Monomers with two or more polymerizable double bonds, which react at different rates during the polymerization.
  • Compounds are preferably used in which at least one reactive group polymerizes at about the same rate as the other monomers, while the other reactive group (or reactive groups) e.g. polymerizes much slower (polymerize).
  • the different polymerization rates result in a certain proportion of unsaturated double bonds in the rubber. If a further phase is subsequently grafted onto such a rubber, the double bonds present in the rubber react at least partially with the graft monomers to form chemical bonds, i.e. the grafted phase is at least partially linked to the graft base via chemical bonds.
  • graft-crosslinking monomers examples include monomers containing allyl groups, in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyifumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
  • allyl groups in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyifumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
  • graft-crosslinking monomers for further details, reference is made here, for example, to US Pat. No. 4,148,846.
  • the proportion of these crosslinking monomers in the impact-modifying polymer is up to 5% by weight, preferably not more than 3% by weight, based on the impact-modifying polymer.
  • Some preferred emulsion polymers are listed below.
  • graft polymers in particular ABS and / or ASA polymers in amounts of up to 40% by weight, are preferably used for impact modification of PBT, optionally in a mixture with up to 40% by weight of polyethylene terephthalate.
  • Corresponding blend products are available under the trademark Ultradur®S (formerly Ultrablend®S from BASF AG).
  • graft polymers with a multi-layer structure instead of graft polymers with a multi-layer structure, homogeneous, i.e. single-shell elastomers of buta-1,3-diene, isoprene and n-butyl acrylate or their copolymers are used. These products can also be produced by using crosslinking monomers or monomers with reactive groups.
  • emulsion polymers examples include n-butyl acrylate / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers, graft polymers with an inner core of n-butyl acrylate or based on butadiene and an outer shell the aforementioned copolymers and copolymers of ethylene with comonomers which provide reactive groups.
  • the elastomers described can also be made by other conventional methods, e.g. by suspension polymerization.
  • Silicone rubbers as described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290 are also preferred.
  • Fibrous or particulate fillers D are carbon fibers, glass fibers, glass spheres, amorphous silica, asbestos, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar, which are present in amounts of up to 50% by weight. , in particular up to 40%.
  • Preferred mixing ratios with component B) are 40-70% by weight of component B) and 65 to 25% by weight of fillers D); preferred mixing ratios B) to D) are from 100: 1 to 2: 1.
  • Carbon fibers, aramid fibers and potassium titanate fibers may be mentioned as preferred fibrous fillers, glass fibers being particularly preferred as E-glass. These can be used as rovings or cut glass in the commercially available forms.
  • the fibrous fillers can be surface-pretreated with a silane compound for better compatibility with the thermoplastic.
  • Suitable silane compounds are those of the general formula
  • n is an integer from 2 to 10, preferably 3 to 4 m is an integer from 1 to 5, preferably 1 to 2 k is an integer from 1 to 3, preferably 1
  • Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.
  • the silane compounds are generally used in amounts of 0.05 to 5, preferably 0.5 to 1.5 and in particular 0.8 to 1% by weight (based on E) for surface coating.
  • acicular mineral fillers are understood to be mineral fillers with a pronounced acicular character.
  • An example is needle-shaped wollastonite.
  • the mineral preferably has a UD (length diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 11: 1.
  • the mineral filler may optionally have been pretreated with the abovementioned silane compounds; however, pretreatment is not essential.
  • Kaolin, calcined kaolin, wollastonite, talc and chalk may be mentioned as further fillers.
  • thermoplastic molding compositions according to the invention can contain customary processing aids such as stabilizers, oxidation retardants, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.
  • customary processing aids such as stabilizers, oxidation retardants, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.
  • oxidation retarders and heat stabilizers are sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and their mixtures in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions.
  • UV stabilizers which are generally used in amounts of up to 2% by weight, based on the molding composition.
  • Inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, furthermore organic pigments such as phthalocyanines, quinacridones, perylenes and dyes such as nigrosine and anthraquinones can be added as colorants.
  • Sodium phenylphosphinate, aluminum oxide, silicon dioxide and, preferably, talc can be used as the nucleating agent.
  • Lubricants and mold release agents which are different from C are usually used in amounts of up to 1% by weight. It is preferred to use long-chain fatty acids (e.g. stearic acid or behenic acid), their salts (e.g. Ca or Zn stearate) or montan waxes (mixtures of straight-chain, saturated carboxylic acids with chain lengths of 28 to 32 C atoms) as well as Ca or Na montanate and low molecular weight polyethylene or polypropylene waxes.
  • long-chain fatty acids e.g. stearic acid or behenic acid
  • their salts e.g. Ca or Zn stearate
  • montan waxes mixturetures of straight-chain, saturated carboxylic acids with chain lengths of 28 to 32 C atoms
  • plasticizers are phthalic acid dioctyl ester, phthalic acid dibenzyl ester, phthalic acid butyl benzyl ester, hydrocarbon oils, N- (n-butyl) benzenesulfonamide.
  • the molding compositions according to the invention can also contain 0 to 2% by weight of fluorine-containing ethylene polymers.
  • fluorine-containing ethylene polymers These are polymers of ethylene with a fluorine content of 55 to 76% by weight, preferably 70 to 76% by weight. Examples of these are polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymers or tetrafluoroethylene copolymers with smaller proportions (generally up to 50% by weight) of copolymerizable ethylenically unsaturated monomers. These are described, for example, by Schildknecht in "Vinyl and Related Polymers", Wiley-Verlag, 1952, pages 484 to 494 and by Wall in “Fluorpolymers” (Wiley Interscience, 1972).
  • fluorine-containing ethylene polymers are homogeneously distributed in the molding compositions and preferably have a particle size d 50 (number average) in the range from 0.05 to 10 ⁇ m, in particular from 0.1 to 5 ⁇ m. These small particle sizes can be achieved particularly preferably by using aqueous dispersions of fluorine-containing ethylene polymers and incorporating them into a polyester melt.
  • thermoplastic molding compositions according to the invention can be produced by processes known per se, in which the starting components are mixed in conventional mixing devices such as screw extruders, Brabender mills or Banbury mills and then extruded. After the extrusion, the extrudate can be cooled and crushed. Individual components can also be premixed and then the remaining starting materials can be added individually and / or also mixed.
  • the mixing temperatures are usually 230 to 290 ° C.
  • components B) and optionally C) and / or D) can be mixed, made up and granulated with a polyester prepolymer.
  • the granules obtained are then condensed in the solid phase under inert gas continuously or batchwise at a temperature below the melting point of component A) to the desired viscosity.
  • thermoplastic molding compositions according to the invention are notable for good thermal conductivity and electrical insulation.
  • the surfaces are smooth and versatile (printing, laser-inscribable). Printing / labeling using common methods, for example speed printing or inkjet labeling, is possible without any problems.
  • the molding compositions according to the invention can be labeled using laser light, for example Nd: YAG lasers, in accordance with known methods.
  • the preferred thermal conductivity is at least 0.8 W / mk, in particular 1 W / mk.
  • Component A polybutylene terephthalate with a viscosity number of 130 ml / g and a carboxyl end group content of 34 meq / kg (Ultradur® B 4520 from BASF AG) (VZ measured in 0.5% by weight solution of phenol / o-dichlorobenzene), 1: 1 mixture at 25 ° C., containing 0.65% by weight of pentaerythritol tetrastearate (component C), based on 100% by weight of A).
  • Components A) to D) were mixed in a twin-screw extruder at 250 to 260 ° C. and extruded in a water bath. After granulation and drying, test specimens were injected and tested on an injection molding machine.
  • the MVR was determined in accordance with ISO 11 33, the thermal conductivity in accordance with DIN 52612 on shaped bodies (80 mm in diameter, 4 mm in thickness) had been determined beforehand for 24 hours in a standard climate of 23 ° C./50% atmospheric humidity.
  • the ball indentation hardness was determined according to ISO 2039-1 on moldings (80 mm diameter, 4 mm thick). The compositions according to the invention and the results of the measurements are shown in the table.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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  • Computer Hardware Design (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des matières à mouler thermoplastiques contenant A) 10 à 70 % en poids d'un polyester thermoplastique, B) 30 à 85 % en poids d'un oxyde d'aluminium, C) 0 à 5 % en poids au moins d'un ester ou d'un amide d'acides carboxyliques aliphatiques saturés ou non saturés ayant 10 à 40 atomes de carbone et d'alcools ou d'amines aliphatiques saturés ayant 2 à 40 atomes de carbone, D) 0 à 60 % en poids d'autres adjuvants, la somme des pourcentages en poids des composants A) à D) étant égale à 100 %.
PCT/EP2003/014281 2002-12-19 2003-12-16 Matiere polyester a mouler electriquement isolante et thermoconductrice WO2004056914A1 (fr)

Priority Applications (1)

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AU2003293893A AU2003293893A1 (en) 2002-12-19 2003-12-16 Electrically insulating and thermally conductive polyester molding materials

Applications Claiming Priority (2)

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DE2002160098 DE10260098A1 (de) 2002-12-19 2002-12-19 Elektrisch isolierende und wärmeleitfähige Polyesterformmassen
DE10260098.8 2002-12-19

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Cited By (5)

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WO2010037674A1 (fr) * 2008-10-01 2010-04-08 Tesa Se Composition conductrice de chaleur
CN101522770B (zh) * 2006-10-12 2012-05-23 巴斯夫欧洲公司 导热的聚酯模塑材料
US8530568B2 (en) 2004-10-20 2013-09-10 Basf Se Flowable polyamides with hyperbranched polyesters/polycarbonates
US8552101B2 (en) 2011-02-25 2013-10-08 Sabic Innovative Plastics Ip B.V. Thermally conductive and electrically insulative polymer compositions containing a low thermally conductive filler and uses thereof
US8741998B2 (en) 2011-02-25 2014-06-03 Sabic Innovative Plastics Ip B.V. Thermally conductive and electrically insulative polymer compositions containing a thermally insulative filler and uses thereof

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DE102005002044A1 (de) 2005-01-14 2006-07-20 Basf Ag Fließfähige Polyester mit Hydrolyseschutz
DE102007037316A1 (de) 2007-08-08 2009-02-12 Lanxess Deutschland Gmbh Thermisch leitfähige und elektrisch isolierende thermoplastische Compounds
EP2862894B1 (fr) 2013-10-15 2017-12-27 LANXESS Deutschland GmbH Masse moulable thermoplastique
EP2878619A1 (fr) 2013-12-02 2015-06-03 LANXESS Deutschland GmbH Compositions de polyester
EP2915841A1 (fr) 2014-03-04 2015-09-09 LANXESS Deutschland GmbH Composition de polyester

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US5781412A (en) * 1996-11-22 1998-07-14 Parker-Hannifin Corporation Conductive cooling of a heat-generating electronic component using a cured-in-place, thermally-conductive interlayer having a filler of controlled particle size
US6162849A (en) * 1999-01-11 2000-12-19 Ferro Corporation Thermally conductive thermoplastic
EP1384567A1 (fr) * 2002-07-22 2004-01-28 Polymatech Co., Ltd. Objet moulé en polymère thermiquement conductif et procédé pour le fabriquer

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EP0499585A1 (fr) * 1991-02-14 1992-08-19 Ciba-Geigy Ag Charge pour des résines plastiques ayant une conductivité thermique
US5781412A (en) * 1996-11-22 1998-07-14 Parker-Hannifin Corporation Conductive cooling of a heat-generating electronic component using a cured-in-place, thermally-conductive interlayer having a filler of controlled particle size
US6162849A (en) * 1999-01-11 2000-12-19 Ferro Corporation Thermally conductive thermoplastic
EP1384567A1 (fr) * 2002-07-22 2004-01-28 Polymatech Co., Ltd. Objet moulé en polymère thermiquement conductif et procédé pour le fabriquer

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8530568B2 (en) 2004-10-20 2013-09-10 Basf Se Flowable polyamides with hyperbranched polyesters/polycarbonates
CN101522770B (zh) * 2006-10-12 2012-05-23 巴斯夫欧洲公司 导热的聚酯模塑材料
WO2010037674A1 (fr) * 2008-10-01 2010-04-08 Tesa Se Composition conductrice de chaleur
KR20110065423A (ko) * 2008-10-01 2011-06-15 테사 소시에타스 유로파에아 열전도성 조성물
US8911642B2 (en) 2008-10-01 2014-12-16 Tesa Se Heat conduction composition
KR101630732B1 (ko) * 2008-10-01 2016-06-17 테사 소시에타스 유로파에아 열전도성 조성물
US8552101B2 (en) 2011-02-25 2013-10-08 Sabic Innovative Plastics Ip B.V. Thermally conductive and electrically insulative polymer compositions containing a low thermally conductive filler and uses thereof
US8741998B2 (en) 2011-02-25 2014-06-03 Sabic Innovative Plastics Ip B.V. Thermally conductive and electrically insulative polymer compositions containing a thermally insulative filler and uses thereof

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DE10260098A1 (de) 2004-07-01

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